Chemistry of thermally stable bis(amino)silylenes

This paper provides a comprehensive review of the chemistry of the thermall y stable bis(amino)silylenes Si[(NCH2But)(2)C6H4-1,2] [abbreviated as Si(NN )] 1 and Si[N(Bu-t)CH](2) [abbreviated as Si(N'N')] 2 and the somewhat less stable Si[N(Bu-t)CH2](2) [abbreviated as Si(N "N ")] 3. In a brief introdu ction, comments are made on the importance of transient silylenes in organo silicon chemistry and on thermally stable mononuclear silicon(II) compounds having a coordination number greater than two for silicon. The chemistry o f 1-3 is discussed under the headings: synthesis, molecular and electronic structures, and reactions. The latter are classified into eight categories: (i) nucleophilic additions to an unsaturated organic substrate; (ii) inser tions (oxidative addition reactions to the silylene) into a compound contai ning an O-H, C-CI, C-Br, C-I or B-C bond; (iii) insertions into a main grou p element compound having a M-N (M = Li, Na, K), Li-C, Li-Si, or M'(II)-X ( M' = Ge, Sn or Pb; X = C, N, O or Cl) bond; (iv) insertions into a transiti on metal-X bond; (v) further (see ii) oxidative addition reactions of a cha lcogen or (BuNC)-N-t; (vi) reduction reactions; (vii) silylenes as ligands in transition or 4f block metal chemistry, and (viii) silylenes as electrop hiles. (C) 2001 Elsevier Science B.V. All rights reserved.